Olefin isomerization catalysts and process

ABSTRACT

The activity of olefin isomerization catalysts such as RuCl 2  (Ph 3  P) 3  may be substantially enhanced in the presence of compounds which are readily decarbonylated by RuCl 2  (Ph.sub. 3 P) 3  to form carbonyl derivatives of said catalysts.

RELATED APPLICATIONS

This application is a continuation in part of U.S. Ser. No. 391,895 ,filed Aug. 27, 1973, now abandoned which in turn is a divisionalapplication of U.S. Ser. No. 251,986, filed May 10, 1972, now U.S. Pat.No. 3,855,323 which in turn is a continuation-in-part of U.S. Ser. No,80,750, filed Oct. 14, 1970, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to novel olefin isomerization catalysts, and tomethods for preparing and using the same. More particularly, thisinvention relates to an improved method for isomerizing olefins anddiolefins in the presence of novel metal carbonyl catalysts formed byreacting certain ruthenium complexes with compounds which are readilydecarbonylated in the presence of said complexes. This invention is alsodirected to the novel metal carbonyl catalysts themselves.

It is known that such compounds as RuCl₂ (Ph₃ P)₃ are catalysts for theisomerization of olefins. See, for example, Abley et al. Disc. of FaradySoc., 46, 31, 37 (1968). These reactions, however, are oftencharacterized by very slow reaction rates, thus making such processescommercially impracticable.

There is also taught, in U.S. Pat. No. 3,530,198, a process for thepreparation of olefins from carboxylic acids or their esters comprisingcontacting said acid or ester with a catalyst comprising a Group VIIImetal complexed with an organometallic ligand of phosphorus, arsenic orantimony, to form olefins, carbon monoxide and water or alcohol.However, notwithstanding the presence of CO, olefin and organometalliccatalyst in the reaction medium of this process, no increase inisomerization rate or selectivity is obtained when employing the acid orester starting materials of this patented process in conjunction withthe olefins of the present invention, as demonstrated by certaincomparative examples set forth below. Moreover, as these examples willalso demonstrate, none of the carbonyl complex comprising the novelcatalyst of this invention is formed when this prior art method isemployed.

SUMMARY OF THE INVENTION

It has now been found, in accordance with the present invention, thatthe rate and selectivity of olefin isomerization metal complex catalystsof the formula ##EQU1## wherein X is halogen; and R₁, R₂ and R.sub. 3are a lower alkyl having from 1 to 6 carbon atoms, a cycloalkyl group oran aryl (i.e. phenyl, tolyl, naphthyl, etc.) group, and wherein R₁, R₂and R₃ may be the same or different, may be substantially enhanced byreacting said complexes with organic compounds which are readilydecarbonylated by said complexes (i.e. "CO-donating compounds") to formnovel carbonyl derivatives thereof. These carbonyl derivatives thereof.These carbonyl derivatives formed from said metal complexes and saidcompounds which are decarbonylated are metal carbonyl complexes havingthe formula ##EQU2## wherein X and R₁, R₂ and R₃ are as defined above,and m and n are 2 or 3 , and 0 or 1 respectively, but when m is 3, n is0; and when m is 2n can be 0 or 1, depending upon the olefin or thecompound which is decarbonylated. It is these carbonyl compounds whichcomprise the improved olefin isomerization catalyst of this invention.

These improved catalysts are advantageous in that they permit theisomerization reaction to be carried out at a rapid rate in a highlyselective manner under mild conditions in the absence of air or oxygenwhich tends to deactivate the ruthenium metal complexes over a period oftime. The yields obtained are, in most instances, substantiallyquantitative.

These novel catalysts and process are particularly advantageous in thatthey provide a homogeneous reaction medium under mild conditions to giverapid but selective double-bond isomerization reactions wherein thedouble bond shifts take place in a stepwise manner. In addition,skeletal rearrangements, polymerization and other undesirable sidereactions do not occur to any detectable extent.

Thus, for example, despite the dramatic rise in the reaction rates thereis no loss in selectivity in these isomerizations. For example,cycloalkadienes which are prone to disproportionation when conventionalcatalysts are used (acid, base, heterogeneous metal and some solublecatalysts), are smoothly and rapidly isomerized, as shown in Equations 1and 2. Similarly, vinyl-substituted cyclic hydrocarbons, as shown inEquations 3, 4 and 5, which are prone to give many isomers as well asdisproportionation products, are isomerized to a single exocyclicolefin: ##SPC1##

DESCRIPTION OF THE INVENTION

The novel catalysts of this invention may be conveniently formed and theisomerization process carried out by first dissolving the aforedescribedruthenium metal complex in the olefin which is to be isomerized,followed by addition of the CO-donating compound to form the metalcarbonyl catalysts in situ. The reaction mixture is then heated at atemperature of from about70° to 140°C, and preferably from 90° to 100°Cfor from 12 to 28 hours, and most preferably from 16 to 20 hours, underan inert atmosphere such as nitrogen or helium. The reaction product mayreadily be recovered from the reaction mixture by vacuum distillation orlike methods, leaving the catalyst material which may then be used againin its existing form without further treatment.

It will be understood, of course, that while it is more convenient toform the metal carbonyl catalyst of this invention in situ in the olefinstarting material as described above, it is also contemplated that saidcatalyst may be formed separately in a suitable olefin and then added tothe reaction medium.

The olefin starting materials employed in carrying out this processinclude any isomerizable monoolefin having from 4 to 36 carbon atoms, ordiolefin having from 5 to 40 carbon atoms, as for example the followingmonoolefins and diolefins:

    Monoolefins:       Diolefins:                                                 pentene-1          1,4-cyclohexadiene                                         hexene-1, hexene-2 1,4-cyclooctadiene, 1,5-cyclooctadiene                     heptene-1, heptene-2                                                                             4-vinylcyclohexene-1                                       octene-1, octene-2 1,4-cycloheptadiene                                        vinylcyclohexane   1,4-dihydronaphthalene                                     vinylcyclopentane  1,4-pentadiene                                             vinylcycloheptane  1,4-hexadiene                                              allylcyclohexane   1,4-octadiene 1,5-octadiene, 1,6-octa-                     allylcyclopentane  diene                                                      nonene-1           2-methyl-1,4-pentadiene                                    decene-1, decene-2, decene-3                                                                     5-phenyl-1,4-pentadiene                                    4-methylcyclohexene-1                                                                            de-limonene                                                4-methylcyclopentene-1                                                        4-methylcyclooctene-1                                                         allylbenzene                                                                  propenylbenzene                                                               4-phenylbutene-1                                                          

and like isomerizable olefins.

The aforementioned metal complexes include compounds having the formula##EQU3## wherein X and R₁, R₂ and R₃ are as defined above. Of these, theruthenium compounds of the formula RuCl₂ (Ph₃ P)₃ are preferred, whereinPh is phenyl. The molar concentration of metal complex to be used inaccordance with the invention is not critical, but it desirably in therange of from 10.sup.⁻² to 10.sup.⁻⁴ moles of catalyst per liter ofolefin, and preferably about 10¹¹⁶ 3 moles. Larger amounts may beemployed but are not necessary.

The organic CO-donating compounds are, as mentioned above, thosecompounds which decarbonylate readily in the presence of the above metalcomplexes to form carbonyl derivatives of said metal complexes. Includedamongst those materials are carbon monoxide, ethylene oxide, styreneoxide, butadiene monoxide, phenylacetaldehyde, benzaldehyde,crotonaldehyde, epoxides, formic acid esters such as benzyl formate,alcohols and related materials. However, other carboxylic acids thanformic acid, such as acetic acid and higher homologues thereof, andtheir esters, are not effective CO-donating compounds for purposes ofthis invention. When carbon monoxide is employed as the carbonylcompound, it is desirable to bubble a stream of this gas through theolefin prior to addition of the metal complex. The amount and manner inwhich carbon monoxide is added should be carefully regulated to avoidformation of a catalytically inactive dicarbonyl complex. Generally,however, the molar concentration of the carbonyl-donating compounds mayvary from 10.sup.⁻¹ to 10.sup.⁻³ moles of compound per liter of olefin,and preferably about 10.sup.⁻² moles.

In a further embodiment of this invention, it has been found thatruthenium complexes having arsine ligands may be substituted for theruthenium phosphine complexes described above as starting materials inthe preparation of the improved catalysts of this invention. Thus, ithas been found that complexes of the formula ##EQU4## wherein X and R₁ ,R₂ and R₃ are as defined above, L is a low molecular weight alcohol orketone such as methanol, ethanol, acetone or the like, a is 2 to 4, andb is 0 or 1, when contacted in the same manner and with the same organiccompounds described above which are readily decarbonylated to formeffective olefin isomerization catalysts of the formula ##EQU5## whereinX, R₁, R₂ and R₃ are as defined above, and wherein m and n are 2 or 3,and 0 or 1, respectively, but when m is 3, n is 0; and when m is 2, ncan be 0 or 1, depending upon the olefin or the compound which isdecarbonylated.

These above-described ruthenium arsine complexes used in the preparationof the improved catalysts of this invention are prepared by contacting aruthenium halide with the respective substituted arsine compound in alower molecular weight alcohol or ketone solvent. Thus, depending uponthe precise nature of the R₁, R₂ and R₃ compounds as well as the solventemployed, the number of arsine groups and "L" groups will varyaccordingly.

The following examples are provided to illustrate the novel processesand products of this invention.

EXAMPLE 1

Carbon monoxide was bubbled rapidly through pure 4-vinylcyclohexene(free of oxygen or hydroperoxides) for 30 seconds. The4-vinylcyclohexene had been purified by distillation under nitrogenfollowed by percolation through activated silica gel under nitrogen. Theolefin, 10 ml., was added to 0.062 gm. of [RuCl₂ (Ph₃ P)₃ ] and themixture stirred under nitrogen for 18.5 hours. After this time thereaction mixture was allowed to cool to room temperature and g.l.p.c.analysis showed 23.2 percent isomerization has occured (see Table I forisomer distribution). A similar experiment carried out in the absence ofCO gave less than 1.5 percent isomerization after 20 hours. Introductionof CO, therefore, gave a 15-fold increase in the percent ofisomerization.

An orange complex (m.p.=190°C dec.) having the following composition:

    RuCl.sub.2 (CO) (P Ph.sub.3).sub.2 . (C.sub.8 H.sub.12)

was precipitated in 40 percent yield (0.025 gm) after reaction by adding50 ml. of n-pentane to the reaction mixture. The infrared spectrum[νCO=5.1μ(vs);νPh₃ P=9.1μ(s)] showed that this material was a carbonylcomplex. It was capable of isomerizing pure 4-vinylcyclohexene at arapid rate even in the absence of added CO. The results of this run aresummarized in Table I.

EXAMPLE 2

According to the procedures of Example 1, ethylene oxide was bubbledthrough 10 ml. of pure 4-vinylcyclohexene for 30 seconds prior toaddition of 0.062 gm. [RuCl₂ (Ph₃ P)₃ ]. After stirring at 100°C undernitrogen for 19.5 hours g.l.p.c. analysis showed that 99.8 percentisomerization had occurred as compared with <1.5 percent withoutethylene oxide. Addition of 50 ml. n-pentane to the reaction mixtureprecipitated 0.0062 gm. (10 percent yield) of a brown soild havingabsorptions in the infrared at 5.1 and 9.1 characteristic of Ru--CO and--PPh₃ respectively. The results of this run are summarized in Table I.

EXAMPLE 3

A 5 × 10.sup.⁻² M solution of styrene oxide (10 ml.) in pure (cf.Example 1) 4-vinycyclohexene was added to 0.062 grams of [RuCl₂ (Ph₃ P)₃] and the solution stirred at 100°C under nitrogen for 29 hours. Glpcanalysis showed that the extent of isomerization was 99 percent.Addition of pentane to the reaction mixture gave a tan solid havinginfrared absorptions at 5.1 (Ru-CO) and 9.1 (Ph₃ P). The results of thisrun are summarized in Table I.

EXAMPLE 4

According to the procedure of Example 3, 0.1 ml. of benzylformate, 10.0ml. of 4-vinylcyclohexene, and 0.062 gm. [RuCl₂ Ph₃ ]₃ were stirred at100°C under nitrogen for 19 hours. Isomerization was complete andproducts are listed in Table I. Addition of 50 ml. pentane to thereaction mixture gave 0.036 gm. (58 percent yield) of a tan carbonylν[μ(CO)=5.0μ(s); ν(Ph₃ P)=9.1μ(s)] which decomposed from 137° to 147°C.The results of this run are summarized in Table I.

EXAMPLES 5 to 12

In accordance with the general procedures of the foregoing examples, butvarying the olefin substrate, the CO-donating catalyst, together withthe quantities of catalyst and the reaction times, there were obtainedthe results tabulated below in Table I as Examples 5 to 12, along withthe tabulation of the results of Examples 1 to 4.

In Example 11, the catalyst complex which was formed from RuCl₂ (Ph₃P)₃, allylbenzene (C₉ H₁₀), and CO, was isolated in 40 percent yield andidentified as

    RuCl.sub.2 (Ph.sub.3 P).sub.2.(C.sub.9 H.sub.10).

                                      TABLE I                                     __________________________________________________________________________    The Effect of CO, Aldehydes and Epoxides on Olefin Isomerization by           RuCl.sub.2 (Ph.sub.3 P).sub.3                                                                                        Isomer-                                Ex.     Co-  Time                                                                              Temp                                                                              Ru(II)                                                                             Co-Cat.      ization                                                                           Ruthenium Complex After                                                       Reaction                           No.                                                                              Olefin                                                                             Catalyst                                                                           (Hrs.)                                                                            (°C)                                                                       (M/L).sup.d                                                                        (M/L).sup.d                                                                        Products, (%)                                                                         (%) Color                                                                             IR    m,p.                                                                               Yield(%).C)         __________________________________________________________________________    1  4-VCH.sup.e                                                                        CO   18.5                                                                              100 6.6×10.sup.-.sup.3                                                           .sup.a                                                                             trans-4-ECH,                                                                          23.2                                                                              Orange    ˜190                                                                         40                                                 7.8;            5.1μ(vs)                                                                         dec.                                                    cis-4-ECH,7.7;  9.1μ(s)                                                    trans-3-ECH,                                                                  1.0;                                                                          cis-4-ECH,1.0;                                                                Other, 5.7                                     2  "    Ethylene                                                                           19.5                                                                              100 6.6×10.sup.-.sup.3                                                           .sup.a                                                                             trans-4-ECH,                                                                          99.8                                                                              Brown                                                                             5.1μ(m)                                                                          .sup.c                                                                             10                          oxide                  0.2;            9.1μ(vvs)                                                  cis-4-ECH,0.3;                                                                trans-3-ECH,                                                                  41.1;                                                                         cis-4-ECH,                                                                    52.8;                                                                         ethylcyclohex-                                                                adiene, 4.5;                                                                  Other, 0.9                                     3  "    Styrene                                                                            29.0                                                                              100 6.6×10.sup.-.sup.3                                                           5×10.sup.-.sup.2                                                             cis+trans-ECH,                                                                        99.0                                                                              Tan 5.1μ(vs)                                                                         .sup.c                                                                             .sup.c                      oxide                  1.4;                                                                          trans-3-ECH,                                                                  41.5;                                                                         cis-4-ECH, 51.1;                                                              Other, 4.8                                     4  4-VCH                                                                              Benzyl-                                                                            19.0                                                                              100 6.6×10.sup.-.sup.3                                                           8×10.sup.-.sup.2                                                             cis+trans-4-                                                                          99.8                                                                              Tan 5.0μ(s)                                                                          137-147                                                                            58                          formate                ECH, 0.3;       9.1μ(s)                                                                          dec.                                                    trans-3-ECH,                                                                  43.3;                                                                         cis-3-ECH,                                                                    53.9;                                                                         Other, 2.5                                     5  4-VCH.sup.e                                                                        None 18  100 6.6×10.sup.-.sup.3                                                           --   trans-4-ECH.sup.f,                                                                     1.5                                                                              Gold                                                                              6.4μ(m)                                                                          110-113                                                                            46                                                 0.7;            9.1μ(s)                                                                          →clear                                           cis-4-ECH,0.7;  (doublet)                                                                           melt                                                    Other, 0.1                                     6  "    Phenyl-                                                                            19.5                                                                              100 6.6×10.sup.-.sup.3                                                           5×10.sup.-.sup.2                                                             trans-4-ECH,                                                                          63.5                                                                              Tan 5.1μ(s)                                                                          .sup.c                                                                             59                          acetalde-              12.2;           (doublet)                              hyde.sup.b             cis-4-ECH,14.6; 9.1                                                           trans-3-ECH,                                                                  13.5;                                                                         cis-3-ECH,15.6;                                                               Other, 7.9                                     7  "    Croton-                                                                            29.0                                                                              100 6.6×10.sup.-.sup.3                                                           1×10.sup.-.sup.1                                                             trans-4-ECH,                                                                           9.2                                                                              Tan 5.1μ(vs)                                                                         .sup.c                                                                             .sup.c                      aldehyde               3.5;            9.1μ(s)                                                    cis-4-ECH,3.3;  6.1,6.2(w)                                                    cis+trans-3-                                                                  ECH, 0.9;                                                                     Other, 1.5                                     8  Allyl-                                                                             None 17.0                                                                              100 1×10.sup.-.sup.2                                                             --   cis-propenyl-                                                                          5.5                                                                              Green                                                                             9.1(s)                                                                              ˜225                                                                         .sup.c                 benzene                     benzene, 1.6;                                                                             Brown     dec.                                                    trans-propenyl-                                                               benzene, 3.7;                                                                 Other, 0.2                                                                    (indane)                                       9  "    Ethylene                                                                           19.0                                                                              100 1×10.sup.-.sup.2                                                             .sup.a                                                                             cis-propenyl-                                                                         99.5                                                                              Tan 5.1μ(vs)                                                                         .sup.c                                                                             10                          oxide                  benzene, 5.5;   9.1μ(vs)                                                   trans-propenyl-                                                               benzene, 93.9;                                                                Other, 0.1                                     10 "    Styrene                                                                            17.5                                                                              100 6.6×10.sup.-.sup.3                                                           5×10.sup.-.sup.2                                                             cis-propenyl-                                                                         99.8                                                                              Green                                                                             5.1μ(m)                                                                          >300 15                          oxide                  benzene, 5.0;   9.1μ(vs)                                                   trans-propenyl-                                                               benzene, 94.6;                                                                Other, 0.2                                     11 "    CO   17.0                                                                              100 1×10.sup.-.sup.2                                                             .sup.a                                                                             cis-propenyl-                                                                         53.9                                                                              Red-                                                                              5.1μ(vs)                                                                         270-277                                                                            40                                                 benzene, 24.1;                                                                            Brown                                                                             9.1μ(s)                                                    trans-propenyl-                                                               benzene, 28.5;                                                                Other, 1.3                                                                    (indane)                                       12 4-VCH                                                                              Benz-                                                                              17.0                                                                              100 6.6×10.sup.-.sup.3                                                           9×10.sup.-.sup.2                                                             trans-4-ECH,                                                                          11.3                                                                              Dark                                                                              5.1μ(vs)                                                                              33                          aldehyde               3.7;        tan 9.1μ(s)                                                    cis-4-ECH, 4.2;                                                               trans-3-ECH,                                                                  0.4;                                                                          cis-3-ECH, 0.5;                                                               Other, 2.5                                     __________________________________________________________________________     .sup.a Administered by bubbling the gas rapidly through the olefin for        several minutes prior to addition of catalyst                                 .sup.b 50 percent solution in ethanol                                         .sup.c This data was not obtained                                             .sup.d M/L = moles/liter                                                      .sup.e VCH = vinylcyclohexene                                                 .sup.f ECH = ethylidenecyclohexene                                       

EXAMPLE 13

In accordance with the general procedures of Example 4, 0.062 gms. ofRuCl₂ (PEt₂ Ph)₃, where Et is ethyl and Ph is phenyl, is stirredtogether with 10 ml. of 1-hexene under nitrogen atmosphere at 64PC inthe presence of 0.5 ml. of ethanol for 48 hours. At the end of thatperiod analysis of the reaction product by glpc shows that a mixture ofisomeric hexenes is obtained in good yield, and the complex, RuCl₂(CO)(PEt₂ Ph)₂.(C.sub. 6 H₁₂), where C₆ H₁₂ corresponds to the hexenemoiety, is isolated in the usual manner.

EXAMPLE 14

In accordance with the foregoing procedure, but substituting RuCl₂ (Ph₃As)₂ (CH₃ OH) for RuCl₂ (PEt₂ Ph)₃, there is obtained the same mixtureof isomeric hexenes in good yield.

EXAMPLE 15

In accordance with the procedures of Example 2, vinylcyclopentane wasisomerized to ethylidenecyclopentane (98 percent) and1,4-dihydronaphthalene was isomerized to 1,2-dihydronaphthalene (99percent).

In the former case the complex, RuCl₂ (CO)(PPh₃)₂ .(C₇ H₁₂), where C₇H₁₂ corresponds to the ethylidenecyclopentane moiety, is isolated afterreaction in the usual manner.

EXAMPLE 16

In comparison with the selective formation of 1,2-dihydronaphthalene (99percent) from 1,4-dihydronaphthalene as demonstrated in Example 15,above, when the conditions and starting materials of Example 1 of U.S.Pat. No. 3,530,198 are applied to this compound, the following resultsare obtained:

To 0.5 g palladium chloride, 3 g. triphenylphosphine and 100 g. octanoicacid is added 10 mls. of 1,4-dihydronaphthalene and the mixture refluxedaccording to the procedures of Example 1 of U.S. Pat. No. 3,530,198. Inaddition to the octenes obtained from dicarboxylation, there is observedthe formation of 1,2-dihydronaphthalene -- 38 percent, decalin -- 22percent, naphthalene -- 28 percent and others -- 12 percent. It is notedthat substantial amounts of palladium metal is deposited in the reactionflask.

The following three examples also illustrate the difference in theresults obtained, particularly in the rates to isomerization, when theprocess of the present invention is compared with that of U.S. Pat. No.3,530,198. Thus, the results of Examples 18 and 19, employing one of thecarboxylic acids and esters thereof of that patent in the process of thepresent invention, when compared with the results obtained in Example17, show that the prior art method yields only 5 to 6 percent in a givenperiod while the instant method yields more than 99 percent for the sameperiod.

Moreover, no carbonyl complex was recovered from the reaction medium ofExamples 17 and 18.

EXAMPLE 17

The catalyst, RuCl₂ (Ph₃ P)₃, (0.05 h), was dissolved in 10 ml of4-vinylcyclohexene to which 50 ml of a CO-donor (enumerated below) wasadded. After warming the mixture at 90°C for 24 hours the extent ofisomerization to 3- and 4-ethylidenecyclohexene was determined by glpcanalysis. The results are tabulated below.

    ______________________________________                                        Catalyst  Additive    Temp.    % Reaction 4-VCH                               (50 mg)   (50 l)      (°C.)                                                                           (10 ml) 24 hours                               ______________________________________                                        RuCl.sub.2 (Ph.sub.3 P).sub.3                                                           None        90        5                                             "         Benzylformate                                                                             90       99                                             "         Styrene oxide                                                                             90       99                                             ______________________________________                                    

Analysis showed 58 percent of ruthenium carbonyl complex to be presentwhen benzyl formate was used as the additive.

EXAMPLE 18

The catalyst, RuCl₂ (Ph₃ P)₃, (0.05 g), was dissolved in 10 ml of4-vinylcyclohexene to which various amounts of octanoic acid were added.After warming the mixture at 90°C and 120°C, respectively, for 24 hoursthe extent of isomerization to 3- and 4-ethylidenecyclohexene wasdetermined by glpc analysis. The results are tabulated below.

    ______________________________________                                        Catalyst          Temp.    % Reaction 4-VCH (10 ml)                           (50 mg.) Acid     (°C.)                                                                           6 hours  24 hours                                  ______________________________________                                        RuCl.sub.2 (Ph.sub.3 P).sub.3                                                          None     90       1        5                                         "        5 μ1  90       1        4                                         "        10 μ1 90       1        6                                         "        50 μ1 90       1        3                                         "        10 mls   90       0        0                                         "        10 mls   120      0        1                                         ______________________________________                                    

Analysis failed to reveal the presence of any organometallic rutheniumcarbonyl complex.

EXAMPLE 19

The catalyst, RuCl₂ (Ph₃ P)₃, (0.05 g), was dissolved in 10 ml of4-vinylcyclohexene to which various amounts of ethyl octanoate wereadded. After warming the mixture at 90°C for 24 hours the extent ofisomerization to 3- and 4-ethylidenecyclohexene was determined byg.l.p.c. analysis. The results are tabulated below.

    ______________________________________                                        Catalyst          Temp.    % Reaction 4-VCH (10 ml)                           (50 mg.) Ester    (°C.)                                                                           6 hours  24 hours                                  ______________________________________                                        RuCl.sub.2 (Ph.sub.3 P).sub.3                                                          None     90       1        5                                         "        10 μ1 90       1        6                                         "        50 μ1 90       0.5      1.5                                       "        10 ml    90       2        4                                         ______________________________________                                    

Analysis failed to reveal the presence of any organometallic rutheniumcarbonyl complex.

The invention claimed is:
 1. A compound having the formula ##EQU6##wherein X is halogen; R₁, R₂, and R₃ are lower alkyl groups having from1 to 6 carbon atoms, cycloalkyl, or aryl, wherein R₁, R₂, and R₃ may bethe same or different; and n is 1; and wherein the olefin is anisomerizable monoolefin having from 4 to 36 carbon atoms or diolefinhaving from 5 to 40 carbon atoms.
 2. A compound according to claim 1having the formula

    RuCl.sub.2 (CO) (P Ph.sub.3).sub.2 . (C.sub.8 H.sub.12)

wherein pH is phenyl.
 3. A compound according to claim 1 having theformula

    RuCl.sub.2 (CO) (P Ph.sub.3).sub.2 . (C.sub.9 H.sub.10)

wherein pH is phenyl.
 4. A compound according to claim 1 having theformula

    RuCl.sub.2 (CO) (P Et.sub.2 Ph).sub.2 . (C.sub.6 H.sub.12)

wherein Et is ethyl and Ph is phenyl.
 5. A compound according to claim 1having the formula

    RuCl.sub.2 (CO) (P Ph.sub.3).sub.2 . (C.sub.7 H.sub.12)

wherein pH is phenyl.